US4500697A - Mixture of substances suitable for use as a powder varnish or binder for powder varnishes - Google Patents
Mixture of substances suitable for use as a powder varnish or binder for powder varnishes Download PDFInfo
- Publication number
- US4500697A US4500697A US06/622,180 US62218084A US4500697A US 4500697 A US4500697 A US 4500697A US 62218084 A US62218084 A US 62218084A US 4500697 A US4500697 A US 4500697A
- Authority
- US
- United States
- Prior art keywords
- weight
- powder
- mixture
- binder
- varnish
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000002966 varnish Substances 0.000 title claims abstract description 94
- 239000000843 powder Substances 0.000 title claims abstract description 79
- 239000000203 mixture Substances 0.000 title claims abstract description 73
- 239000000126 substance Substances 0.000 title claims abstract description 25
- 239000011230 binding agent Substances 0.000 title claims abstract description 19
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000005058 Isophorone diisocyanate Substances 0.000 claims abstract description 21
- 239000013638 trimer Substances 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 239000012948 isocyanate Substances 0.000 claims abstract description 13
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 13
- YOQVGIBXRRGAOX-UHFFFAOYSA-N 1-isocyanato-3-(isocyanatomethyl)pentane Chemical compound O=C=NCC(CC)CCN=C=O YOQVGIBXRRGAOX-UHFFFAOYSA-N 0.000 claims abstract description 12
- 150000003673 urethanes Chemical class 0.000 claims abstract description 12
- AHBNSOZREBSAMG-UHFFFAOYSA-N 1,5-diisocyanato-2-methylpentane Chemical compound O=C=NCC(C)CCCN=C=O AHBNSOZREBSAMG-UHFFFAOYSA-N 0.000 claims abstract description 10
- 150000002009 diols Chemical class 0.000 claims abstract description 8
- 150000004072 triols Chemical class 0.000 claims abstract description 7
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229920000728 polyester Polymers 0.000 claims description 27
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 claims description 24
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 12
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 11
- 229920000647 polyepoxide Polymers 0.000 claims description 10
- 239000003822 epoxy resin Substances 0.000 claims description 9
- 125000005442 diisocyanate group Chemical group 0.000 claims description 8
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 claims description 7
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 6
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 5
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 4
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical group OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims description 4
- 238000005829 trimerization reaction Methods 0.000 claims description 4
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical compound C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 claims description 3
- 150000001298 alcohols Chemical class 0.000 claims description 3
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 3
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- XIIHTVOIRWYVJC-UHFFFAOYSA-N 1,5-diisocyanato-1,3,3-trimethylcyclohexane Chemical compound CC1(C)CC(N=C=O)CC(C)(N=C=O)C1 XIIHTVOIRWYVJC-UHFFFAOYSA-N 0.000 claims 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 claims 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 34
- 239000003431 cross linking reagent Substances 0.000 description 28
- 238000000034 method Methods 0.000 description 25
- 239000003795 chemical substances by application Substances 0.000 description 19
- 239000004594 Masterbatch (MB) Substances 0.000 description 18
- 239000004814 polyurethane Substances 0.000 description 18
- 239000012463 white pigment Substances 0.000 description 18
- 239000005056 polyisocyanate Substances 0.000 description 17
- 229920001228 polyisocyanate Polymers 0.000 description 17
- 238000002844 melting Methods 0.000 description 16
- 230000008018 melting Effects 0.000 description 16
- 229920002635 polyurethane Polymers 0.000 description 16
- 238000009472 formulation Methods 0.000 description 15
- 239000002981 blocking agent Substances 0.000 description 10
- 239000011248 coating agent Substances 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 239000004593 Epoxy Substances 0.000 description 8
- 230000000903 blocking effect Effects 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 6
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 6
- 229920001187 thermosetting polymer Polymers 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 239000010408 film Substances 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 238000004383 yellowing Methods 0.000 description 5
- 229940117969 neopentyl glycol Drugs 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- IUVCFHHAEHNCFT-INIZCTEOSA-N 2-[(1s)-1-[4-amino-3-(3-fluoro-4-propan-2-yloxyphenyl)pyrazolo[3,4-d]pyrimidin-1-yl]ethyl]-6-fluoro-3-(3-fluorophenyl)chromen-4-one Chemical compound C1=C(F)C(OC(C)C)=CC=C1C(C1=C(N)N=CN=C11)=NN1[C@@H](C)C1=C(C=2C=C(F)C=CC=2)C(=O)C2=CC(F)=CC=C2O1 IUVCFHHAEHNCFT-INIZCTEOSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 210000003298 dental enamel Anatomy 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 150000003951 lactams Chemical class 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 239000012265 solid product Substances 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000002671 adjuvant Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 150000003852 triazoles Chemical class 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- YXRKNIZYMIXSAD-UHFFFAOYSA-N 1,6-diisocyanatohexane Chemical compound O=C=NCCCCCCN=C=O.O=C=NCCCCCCN=C=O.O=C=NCCCCCCN=C=O YXRKNIZYMIXSAD-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 101100386054 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) CYS3 gene Proteins 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- -1 aromatic dicarboxylic acids Chemical class 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- JJCFRYNCJDLXIK-UHFFFAOYSA-N cyproheptadine Chemical compound C1CN(C)CCC1=C1C2=CC=CC=C2C=CC2=CC=CC=C21 JJCFRYNCJDLXIK-UHFFFAOYSA-N 0.000 description 1
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000009503 electrostatic coating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 101150035983 str1 gene Proteins 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 239000013008 thixotropic agent Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/80—Masked polyisocyanates
- C08G18/8003—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen
- C08G18/8006—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32
- C08G18/8009—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203
- C08G18/8032—Masked aliphatic or cycloaliphatic polyisocyanates not provided for in one single of the groups C08G18/8016 and C08G18/8025
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
- C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
- C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/80—Masked polyisocyanates
- C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
- C08G18/807—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with nitrogen containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2150/00—Compositions for coatings
- C08G2150/20—Compositions for powder coatings
Definitions
- This invention relates to new varnish polyisocyanates having an isocyanurate or urethane structure blocked with blocking agents from a mixture of 2-methyl-1,5-diisocyanatopentane or 2-ethyl-1,4-diisocyanatobutane or 3-isocyanatomethyl-3,5,5-trimethylcyclohexylisocyanate or a mixture thereof, and a process for the production of these new varnish polyisocyanates as well as a process for the use thereof as an isocyanate component for the production of thermosetting polyurethane powder varnishes.
- Polyurethane powder varnishes on the basis of partially or completely blocked polyisocyanates or polymers containing hydroxyl groups whose softening point is above 40° are state-of-the-art and are frequently described in the literature, e.g., in the DE-OSS 21 05 777, 25 42 191, 27 35 497, 28 42 641, 30 04 876, 30 39 824, or 31 28 743.
- Polyurethane powder varnishes essentially consist of a component containing hydroxyl groups and a polyisocyanate whose NCO groups are partially or completely blocked with a blocking agent, so that the OH:NCO polyaddition reaction cannot take place at temperatures below 140° C. Only after heating to temperatures ⁇ 150° C. is it possible to cross-link such powder varnishes to a coating film within a relevant time while setting free the blocking agent and reacting the OH groups with the NCO groups.
- the isocyanato-isocyanurates such as for example hexamethylenediisocyanate (short: HDI)
- HDI hexamethylenediisocyanate
- products can be produced by mixed trimerization of these two polyisocyanates (HDI/IPDI), which in their blocked form, cf. page 8, lines 16-21, are suitable for the production of polyurethane powder varnishes even though this has not been proved by experiments. It is therefore possible to vary the melting points by means of the mole ratio of the diisocyanates. Moreover, among other things the improved solvent compatibility and flexibility at low temperatures are pointed out, cf. page 3, lines 19-21.
- thermosetting polyurethane baking enamels do not show any yellowing phenomena at temperatures below those required for hardening the coating films, since otherwise, in case of technical trouble (e.g., assembly-line stoppage), during the thermosetting process more or less large quality reductions (discolorations) must be expected. In the past, this has not always been guaranteed.
- polyisocyanates which, although partially or totally blocked, are suitable for use as cross-linking agents in polyurethane powder varnishes and which are susceptible to grinding. It is further required that these polyisocyanates be thermally and oxidatively stable and not contribute to yellowing of the thermosetting polyurethane baking enamels.
- polyisocyanates which, although partially or totally blocked, are suitable for use as cross-linking agents in polyurethane powder varnishes and which are susceptible to grinding.
- the foregoing and other objects are attained by providing a mixture of substances suitable as a powder varnish or a binder for powder varnishes containing an isocyanate component having partially or totally blocked isocyanate groups, and a polyhydroxyl component, wherein the isocyanate component contains trimers or a mixture of trimers from a mixture containing 2-methyl-1,5-diisocyanatopentane (MPDI) and 2-ethyl-1,4-diisocyanatobutane (EBDI) according to the formulas (I) and (II) ##STR1## and having about 88 to 99% by weight of (I) and about 12 to 1% by weight of (II) in combination with 3-isocyanatomethyl-3,5,5-trimethylcyclohexylisocyanate (IPDI), isocyanato-isocyanurate trimers or mixtures thereof, mixed urethane adducts or a mixture of the urethane adduct
- the mixture of the present invention consists mainly of 2-methyl-1,5-diisocyanatopentane (MPDI) and 2-ethyl-1,4-diisocyanatobutane (EBDI), in the amounts of about 88 to 99% by weight of 2-methyl-1,5-diisocyanatopentane and about 12 to 1% by weight of 2-ethyl-1,4-diisocyanatobutane, combined with 3-isocyanatomethyl-3,5,5-trimethylcyclohexylisocyanate, isocyanatoisocyanurate trimers or mixtures thereof, mixed urethane adducts or a mixture of the urethane adducts obtained from the reaction of the mixture of (I) and (II) and (I
- the ratio of diisocyanates used for trimerization or urethane adduct formation, MPDI/EBDI mixture to IPDI, is between about 90 to 10 or 10 and 90% by weight, respectively, preferably between about 75 and 25 or 25 and 75% by weight, respectively.
- the cross-linking agents according to the invention have a latent NCO content of about 7-18% by weight, preferably about 9-15% by weight and a free NCO content of ⁇ 3% by weight, preferably ⁇ 2% by weight.
- the principle components of the mixture according to the present invention are:
- IPDI 3-isocyanatomethyl-3,5,5-trimethylcyclohexylisocyanate
- the polymers containing hydroxyl groups are epoxy resins, acrylates and especially polyesters, the basis of which are predominantly aromatic dicarboxylic acids, diols and triols in polyurethane powder varnishes.
- a particular object of the present invention is the use of the mixture of substances as powder varnishes or as binders for powder varnishes for the coating of any thermosetting substrates according to coating methods known in the art which are suitable for the processing of powder varnishes.
- the blocked polyisocyanates according to the invention and the polymers containing hydroxyl groups optionally are formulated by means of conventional technologies into sprayable powders while adding the admixtures customary in PUR chemistry, applied by electrostatic coating and baked at between about 140° and 250° C., preferably between about 160° and 200° C.
- the mixing ratio can vary widely.
- the best varnish technical characteristics are maintained if the binder ratio consists of about 9-45% by weight of cross-linking agents and about 55-91% by weight of polyesters, whereby the OH/NCO ratio can be set at about 1:0.8 to 1:1.2, preferably about 1:0.95 to 1:1.1. It is particularly recommended to use an equivalent NCO of the cross-linking agent per OH equivalent of the polyhydroxyl compound.
- trimers from the mixture consisting of MPDI/EBDI and IPDI in said ratios were produced in the known manner according to the instructions of GB-PS 1 391 066, DE-OSS 23 25 826, 26 44 684 or 29 16 201.
- the products of the process consist of isocyanato-isocyanurate with optionally higher oligomers and have an NCO content of 14-22% by weight, preferably 15-20.5% by weight, which is reduced to an NCO content of ⁇ 3% by weight, preferably ⁇ 2% by weight, by blocking with blocking agents known in the art, especially ⁇ -caprolactam or 1H-1,2,4-triazole.
- Trimerization can take place in substance (neat) or in an inert organic solvent.
- the catalytic reaction should be stopped as soon as the NCO content of the mixture indicates that about 30-50% of the NCO groups are reacted.
- the diisocyanate that has not been reacted is subsequently separated together with the catalyst and optionally with the solvent.
- the products of the process can also be based on the reaction of said diisocyanate--(MPDI/EBDI mixture to IPDI)--ratios in combination with diols and triols, especially with trimethylolpropane (TMP).
- TMP trimethylolpropane
- the reactants are preferably reacted in such ratios that one NCO group is reacted per OH group.
- the isocyanate component is provided and the blocking agent is added in portions.
- the reaction takes place at temperatures below the decomposition temperature at 90°-130° C.
- the catalysts usual in PUR chemistry can also be added in a quantity of 0.001-1% by weight in relation to the total mixture.
- Suitable blocking agents are, e.g., phenols, alcohols, acetoacetic esters, lactams, especially ⁇ -caprolactam, as well as triazoles, especially the 1H-1,2,4 triazole that raises the melting point.
- polyesters especially suitable as resins containing hydroxyl groups are polyesters, epoxy resins as well as acrylate containing hydroxyl groups with a molecular weight of about 800-10,000, preferably about 1,200-5,000, a hydroxyl number of 20-150 mg KOH/g, preferably 30-100 mg KOH/g and melting points above 60° C., preferably between 70° C. and 100° C.
- polyesters of terephthalic acid with the alcohols hexamethylene glycol, neopentyl glycol, 1,4-dimethanolcyclohexane and 2,2,2-trimethylolpropane are particularly suitable for the production of powder varnishes.
- the usable epoxy resins are listed in the DE-OS 29 45 113, page 12, line 1, to page 13, line 26.
- Suitable polyacrylates are described in the DE-OS 30 30 539, page 14, line 21, to page 15, line 26.
- the resins containing hydroxyl groups are used in such quantities that the OH/NCO ratio is 1:0.8 to 1:1.2, preferably 1:0.95 to 1:1.1.
- an OH/NCO ratio of 1:0.25 to 1:0.75, preferably 1:0.35 to 1:0.55 is recommended.
- the usual adjuvants and additives include leveling agents, pigments, dyes, fillers, catalysts, thixotropic agents, ultraviolet and oxidation stabilizers.
- the quantity of these substances can vary widely in relation to the quantity of the solid binders.
- the powdery coating agents are produced, e.g., by mixing the solid resins, polyesters and/or epoxy resin and/or acrylate resin and the blocked polyisocyanates, optionally in combination with the required admixtures, in said quantity ratios and extruded at a higher temperature.
- This temperature must be higher than the melting point of polyester/epoxy/acrylate or blocked polyisocyanate or below the decomposition temperature of the cross-linking agents.
- Cooling down follows extruding; then comes grinding to a particle size smaller than 0.25 mm, preferably ⁇ 100 ⁇ . Thereafter, the larger fractions are removed by sifting and returned to the mill.
- the powder ready for spraying to the body to be coated according to known methods is applied, e.g., by electrostatic powder spraying or electrostatic whirl sintering. Subsequently, the varnished objects are baked for 60 minutes to 1 minute in the temperature range of 140°-250° C., preferably 30 to 8 minutes between 160° and 200° C.
- all substrates are suitable that tolerate the cited hardening conditions without loss of the mechanical properties, e.g., metals, glass, ceramic or plastic.
- the polyurethane powder varnishes obtained are distinguished from the known ones by better performance in the presence of heat, ultraviolet-ray and chemical influences.
- the free NCO content was ⁇ 0.8% by weight and the practical latent NCO content was about 12.3% by weight.
- Table 1 provides a survey of composition, physical and chemical properties of additional blocked isocyanato-isocyanurates.
- IPDI-T 1890 commercial product of the Chem. Werke Huels 100 parts by weight of IPDI isocyanurate (IPDI-T 1890 commercial product of the Chem. Werke Huels) with an NCO content of 17.5% by weight and 100 parts by weight of MPDI/EBDI trimer were homogenized at 100°-110° C.
- the NCO content of the melt amounted to 18.1% by weight.
- Blocking with the stoichiometric quantity of ⁇ -caprolactam resulted in a brittle, grindable product with a practical latent NCO content of 11.8% by weight and a melting range of 74°-76° C.
- Table 2 provides a survey on composition, chemical and physical properties of additional blocked urethane adducts.
- the urethane adduct on HDI basis produced in conformance with example 13 was soft and stickly after blocking with ⁇ -caprolactam at room temperature.
- Ts The initial components--terephthalic acid (Ts), dimethylterephthalate (DMT), hexamethylene glycol (HD), neopentylglycol (NPG), 1,4-dimethylolcyclohexane (DMC) and trimethylolpropane (TMP) were put into a reactor and heated by means of an oil bath. After the substances had been largely melted, 0.05% by weight of di-n-butyltin oxide was added as a catalyst at a temperature of 160° C. The first methanol separtion occurred at a temperature of about 170° C. Within 6-8 hours, the temperature was raised to 220°-230° C. and the reaction was completed within another 12 hours. The polyester was cooled to 200° C. and the volatile parts largely removed within 30-45 minutes by forming a vacuum (1 Hg). During the entire reaction time, the bottom product was stirred and a weak N 2 current was directed through the reactin mixture.
- Ts trimethylolpropane
- the ground products, cross-linking agents, polyesters, leveling agents* Masterbatch are thoroughly mixed optionally with the white pigment and optionally fillers in an edge mill and then homogenized in the extruder at 100°-130° C. After cooling, the extrudate is crushed and ground by means of a disk mill to a particle size of ⁇ 100 ⁇ .
- the powder so produced is applied to degreased, optionally prepared sheet iron with an electrostatic powder sprayer at 60 KV and baked in a circulating dried at temperature between 160° and 200° C.
- Imp. rev. impact reverse in inch ⁇ lb
- the powder varnish was produced in accordance with the following formulation, applied and baked between 160° and 200° C.
- the powder varnish was produced in accordance with the following formulation, applied and baked between 160° and 200° C.
- the powder varnish was produced in accordance with the following formulation, applied and baked between 160° and 200° C.
- the powder varnish was produced in accordance with the following formulation, applied and baked between 160° and 200° C.
- the powder varnish was produced in accordance with the following formulation, applied and baked between 160° and 200° C.
- the powder varnish was produced in accordance with the following formulation, applied and baked between 160° C. and 200° C.
- the powder varnish was produced in accordance with the following formulation, applied and baked between 160° C. and 200° C.
- the powder varnish was produced in accordance with the following formulation, applied and baked between 160° C. and 200° C.
- the powder varnish was produced in accordance with the following formulation, applied and baked between 160° C. and 200° C.
- the ready-to-spray powder has lower storage stability and the coating films result in more yellowing under thermal stress.
- the powder varnish was produced in accordance with the following formulation, applied and baked between 160° C. and 200° C.
- thermo-oxidative instability In addition to greater thermo-oxidative instability, greater proneness to chalking was noted following treatment with ultraviolet light.
- the powder varnish was produced in accordance with the following formulation, applied and baked between 160° C. and 200° C.
- the powder varnish was produced in accordance with the following formulation, applied and baked between 160° C. and 200° C.
- the powder varnish was produced in accordance with the following formulation, applied and baked between 160° C. and 200° C.
- the powder varnish was produced in accordance with the following formulation, applied and baked between 160° C. and 200° C.
- thermo-oxidation instability In addition to greater thermo-oxidation instability, greater proneness to chalking was noted also after treatment in ultraviolet light.
- the powder varnish was produced in accordance with the following formulation, applied and baked between 160° C. and 200° C.
- Dian 2,2-bis(4-hydroxylphenyl)propane
- epichlorohydrin Two epoxy resins based on an adduct made of 2,2-bis(4-hydroxylphenyl)propane (Dian) and epichlorohydrin were used, which were first subjected to HCl separation and then reacted with additional Dian.
- the epoxy resins had the following physical data:
- the powder varnish with the following recipe was produced, applied and baked between 180°-200° C.
- the powder varnish with the following recipe was produced, applied and baked between 180° C.-200° C.
- leveling agent Masterbatch 10% Modaflow in epoxy according to D 1.1
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Paints Or Removers (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
A mixture of substances suitable as a powder varnish or a binder for powder varnishes containing an isocyanate component with partially or totally blocked isocyanate groups, and a polyhydroxyl component, wherein mixed trimers or mixtures of individual trimers are used as the isocyanate component from a mixture of 2-methyl-1,5-diisocyanato-pentane (MPDI) and 2-ethyl-1,4-diisocyanatobutane (EBDI) in the amounts of 88 to 99% by weight of (MPDI) and about 12 to 1% by weight of (EBDI), in combination with 3-isocyanato-3,5,5-trimethylcyclohexylioscyanate (IPDI) or mixed urethane adducts obtained from the reaction of the (MPDI/EBDI) mixture in combination with (IPDI) with diols, triols or a mixture thereof.
Description
1. Field of the Invention:
This invention relates to new varnish polyisocyanates having an isocyanurate or urethane structure blocked with blocking agents from a mixture of 2-methyl-1,5-diisocyanatopentane or 2-ethyl-1,4-diisocyanatobutane or 3-isocyanatomethyl-3,5,5-trimethylcyclohexylisocyanate or a mixture thereof, and a process for the production of these new varnish polyisocyanates as well as a process for the use thereof as an isocyanate component for the production of thermosetting polyurethane powder varnishes.
2. Description of the Prior Art:
Polyurethane powder varnishes on the basis of partially or completely blocked polyisocyanates or polymers containing hydroxyl groups whose softening point is above 40° are state-of-the-art and are frequently described in the literature, e.g., in the DE-OSS 21 05 777, 25 42 191, 27 35 497, 28 42 641, 30 04 876, 30 39 824, or 31 28 743.
Polyurethane powder varnishes essentially consist of a component containing hydroxyl groups and a polyisocyanate whose NCO groups are partially or completely blocked with a blocking agent, so that the OH:NCO polyaddition reaction cannot take place at temperatures below 140° C. Only after heating to temperatures ≧150° C. is it possible to cross-link such powder varnishes to a coating film within a relevant time while setting free the blocking agent and reacting the OH groups with the NCO groups.
Not all polyisocyanates are suitable for such purposes and in view of the application as powder materials, there are quite a number of restrictions, especially if the polyisocyanates, partially or completely blocked with the usual blocking agents, themselves have characteristics that make grindability more difficult, so that their use in powder varnishes is greatly limited if not impossible, even though their varnish technical as well as chemical and physical characteristics may be very good.
Thus, normally the isocyanato-isocyanurates, such as for example hexamethylenediisocyanate (short: HDI), are liquid as are their reaction products with blocking agents, as described in EP 0 047 452, corresponding to DE-OS 30 33 860, from page 2, line 29 to page 3, line 6, and cannot be used in powder varnishes. An exception is the isocyanato-isocyanurate of 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate, also called isophoronediisocyanate, short IPDI. It is solid and has a melting range of 102°-104° C. As is further shown in EP 0 047 452, products can be produced by mixed trimerization of these two polyisocyanates (HDI/IPDI), which in their blocked form, cf. page 8, lines 16-21, are suitable for the production of polyurethane powder varnishes even though this has not been proved by experiments. It is therefore possible to vary the melting points by means of the mole ratio of the diisocyanates. Moreover, among other things the improved solvent compatibility and flexibility at low temperatures are pointed out, cf. page 3, lines 19-21.
Furthermore, in practice the thermal and oxidative stability are of decisive importance, so that thermosetting polyurethane baking enamels do not show any yellowing phenomena at temperatures below those required for hardening the coating films, since otherwise, in case of technical trouble (e.g., assembly-line stoppage), during the thermosetting process more or less large quality reductions (discolorations) must be expected. In the past, this has not always been guaranteed.
Therefore, a need clearly continues to exist for polyisocyanates which, although partially or totally blocked, are suitable for use as cross-linking agents in polyurethane powder varnishes and which are susceptible to grinding. It is further required that these polyisocyanates be thermally and oxidatively stable and not contribute to yellowing of the thermosetting polyurethane baking enamels.
Accordingly, it is an object of the present invention to provide polyisocyanates which, although partially or totally blocked, are suitable for use as cross-linking agents in polyurethane powder varnishes and which are susceptible to grinding.
It is also an object of this invention to provide polyisocyanates which, although partially or totally blocked, are thermally and oxidatively stable when used in thermosetting polyurethane baking enamels and do not exhibit yellowing at temperatures below those required for hardening the coating films.
Further, it is a particular object of the present invention to provide a mixture of substances which are suitable as a powder varnish or a binder for powder varnishes, which do not exhibit yellowing at temperatures below those required for hardening the coating films.
According to the present invention, the foregoing and other objects are attained by providing a mixture of substances suitable as a powder varnish or a binder for powder varnishes containing an isocyanate component having partially or totally blocked isocyanate groups, and a polyhydroxyl component, wherein the isocyanate component contains trimers or a mixture of trimers from a mixture containing 2-methyl-1,5-diisocyanatopentane (MPDI) and 2-ethyl-1,4-diisocyanatobutane (EBDI) according to the formulas (I) and (II) ##STR1## and having about 88 to 99% by weight of (I) and about 12 to 1% by weight of (II) in combination with 3-isocyanatomethyl-3,5,5-trimethylcyclohexylisocyanate (IPDI), isocyanato-isocyanurate trimers or mixtures thereof, mixed urethane adducts or a mixture of the urethane adducts obtained from the reaction of the mixtures of (I) and (II) and (IPDI) with diols and triols.
According to the present invention, it has now been surprisingly found that it is possible to attain polyisocyanates which, although partially or totally blocked, are suitable for use as cross-linking agents in polyurethane powder varnishes. The mixture of the present invention consists mainly of 2-methyl-1,5-diisocyanatopentane (MPDI) and 2-ethyl-1,4-diisocyanatobutane (EBDI), in the amounts of about 88 to 99% by weight of 2-methyl-1,5-diisocyanatopentane and about 12 to 1% by weight of 2-ethyl-1,4-diisocyanatobutane, combined with 3-isocyanatomethyl-3,5,5-trimethylcyclohexylisocyanate, isocyanatoisocyanurate trimers or mixtures thereof, mixed urethane adducts or a mixture of the urethane adducts obtained from the reaction of the mixture of (I) and (II) and (IPDI) with diols and triols, especially trimethylolpropane (TMP) and with blocking agents, particularly ε-caprolactam or 1H-1,2,4-triazole-blocked varnish polyisocyanates, which are used especially as cross-linking agents in polyurethane powder varnishes because of their brittle, grindable form.
The ratio of diisocyanates used for trimerization or urethane adduct formation, MPDI/EBDI mixture to IPDI, is between about 90 to 10 or 10 and 90% by weight, respectively, preferably between about 75 and 25 or 25 and 75% by weight, respectively.
The cross-linking agents according to the invention have a latent NCO content of about 7-18% by weight, preferably about 9-15% by weight and a free NCO content of ≧3% by weight, preferably ≧2% by weight.
The principle components of the mixture according to the present invention are:
a. an isocyanate component with partially or completely blocked isocyanate groups,
b. a polyhydroxyl component and
c. optionally, conventional adjuvants and additives,
wherein the mixed trimers or mixtures of the individual trimers from a mixture consisting predominantly of 2-methyl-1,5-diisocyanatopentane (MPDI) and 2-ethyl-1,4-diisocyanatobutane (EBDI) of formulas I and II below ##STR2## have the following composition: 88-99% by weight of 2-methyl-1,5-diisocyanatopentane
12-1% by weight of 2-ethyl-1,4-diisocyanatobutane,
and are applied in combination with 3-isocyanatomethyl-3,5,5-trimethylcyclohexylisocyanate (IPDI) or mixed urethane adducts or a mixture of the individual urethane adducts from the reaction of the MPDI/EBDI mixture in combination with IPDI with diols and/or triols.
The polymers containing hydroxyl groups are epoxy resins, acrylates and especially polyesters, the basis of which are predominantly aromatic dicarboxylic acids, diols and triols in polyurethane powder varnishes.
A particular object of the present invention is the use of the mixture of substances as powder varnishes or as binders for powder varnishes for the coating of any thermosetting substrates according to coating methods known in the art which are suitable for the processing of powder varnishes.
The blocked polyisocyanates according to the invention and the polymers containing hydroxyl groups optionally are formulated by means of conventional technologies into sprayable powders while adding the admixtures customary in PUR chemistry, applied by electrostatic coating and baked at between about 140° and 250° C., preferably between about 160° and 200° C.
The mixing ratio can vary widely. The best varnish technical characteristics are maintained if the binder ratio consists of about 9-45% by weight of cross-linking agents and about 55-91% by weight of polyesters, whereby the OH/NCO ratio can be set at about 1:0.8 to 1:1.2, preferably about 1:0.95 to 1:1.1. It is particularly recommended to use an equivalent NCO of the cross-linking agent per OH equivalent of the polyhydroxyl compound.
The trimers from the mixture consisting of MPDI/EBDI and IPDI in said ratios were produced in the known manner according to the instructions of GB-PS 1 391 066, DE-OSS 23 25 826, 26 44 684 or 29 16 201. The products of the process consist of isocyanato-isocyanurate with optionally higher oligomers and have an NCO content of 14-22% by weight, preferably 15-20.5% by weight, which is reduced to an NCO content of ≦3% by weight, preferably ≦2% by weight, by blocking with blocking agents known in the art, especially ε-caprolactam or 1H-1,2,4-triazole.
Trimerization can take place in substance (neat) or in an inert organic solvent. The catalytic reaction should be stopped as soon as the NCO content of the mixture indicates that about 30-50% of the NCO groups are reacted. The diisocyanate that has not been reacted is subsequently separated together with the catalyst and optionally with the solvent.
The products of the process can also be based on the reaction of said diisocyanate--(MPDI/EBDI mixture to IPDI)--ratios in combination with diols and triols, especially with trimethylolpropane (TMP). Prior to the reaction with blocking agents, they have an NCO content of 11-19% by weight, preferably 13-17% by weight and after blocking ≦3% by weight, preferably ≦2% by weight. The reactants are preferably reacted in such ratios that one NCO group is reacted per OH group.
To carry out the blocking reaction, the isocyanate component is provided and the blocking agent is added in portions. The reaction takes place at temperatures below the decomposition temperature at 90°-130° C. For the isocyanate polyaddition reaction, the catalysts usual in PUR chemistry can also be added in a quantity of 0.001-1% by weight in relation to the total mixture.
Suitable blocking agents are, e.g., phenols, alcohols, acetoacetic esters, lactams, especially ε-caprolactam, as well as triazoles, especially the 1H-1,2,4 triazole that raises the melting point.
The products of the process according to the invention in their use as cross-linking agents for polyurethane powder varnishes are combined with the resins usual for powder varnishes on a polyurethane basis, i.e., preferably with resins containing hydroxyl groups.
Especially suitable as resins containing hydroxyl groups are polyesters, epoxy resins as well as acrylate containing hydroxyl groups with a molecular weight of about 800-10,000, preferably about 1,200-5,000, a hydroxyl number of 20-150 mg KOH/g, preferably 30-100 mg KOH/g and melting points above 60° C., preferably between 70° C. and 100° C.
Preferably suitable for the production of powder varnishes are the polyesters of terephthalic acid with the alcohols hexamethylene glycol, neopentyl glycol, 1,4-dimethanolcyclohexane and 2,2,2-trimethylolpropane.
The usable epoxy resins are listed in the DE-OS 29 45 113, page 12, line 1, to page 13, line 26. Suitable polyacrylates are described in the DE-OS 30 30 539, page 14, line 21, to page 15, line 26.
The resins containing hydroxyl groups are used in such quantities that the OH/NCO ratio is 1:0.8 to 1:1.2, preferably 1:0.95 to 1:1.1. When epoxies are used, an OH/NCO ratio of 1:0.25 to 1:0.75, preferably 1:0.35 to 1:0.55 is recommended.
The usual adjuvants and additives include leveling agents, pigments, dyes, fillers, catalysts, thixotropic agents, ultraviolet and oxidation stabilizers. The quantity of these substances can vary widely in relation to the quantity of the solid binders.
The powdery coating agents are produced, e.g., by mixing the solid resins, polyesters and/or epoxy resin and/or acrylate resin and the blocked polyisocyanates, optionally in combination with the required admixtures, in said quantity ratios and extruded at a higher temperature. This temperature must be higher than the melting point of polyester/epoxy/acrylate or blocked polyisocyanate or below the decomposition temperature of the cross-linking agents.
Cooling down follows extruding; then comes grinding to a particle size smaller than 0.25 mm, preferably <100μ. Thereafter, the larger fractions are removed by sifting and returned to the mill.
The powder ready for spraying to the body to be coated according to known methods is applied, e.g., by electrostatic powder spraying or electrostatic whirl sintering. Subsequently, the varnished objects are baked for 60 minutes to 1 minute in the temperature range of 140°-250° C., preferably 30 to 8 minutes between 160° and 200° C.
For coating with the powdery coating agent, according to the invention, all substrates are suitable that tolerate the cited hardening conditions without loss of the mechanical properties, e.g., metals, glass, ceramic or plastic.
The polyurethane powder varnishes obtained are distinguished from the known ones by better performance in the presence of heat, ultraviolet-ray and chemical influences.
The present invention will be further illustrated by certain examples and references which are provided for purposes of illustration only and are not intended to limit the present invention.
444 parts by weight of IPDI and 336 parts by weight of MPDI/EBDI mixture (94:6) and 0.15 parts by weight of a catalyst (triethylenediamine/propylene oxide 1:1) were mixed at 80° C. with vigorous stirring. In doing so, heat of reaction occurred immediately, whereby the temperature of the reaction mixture rose to about 95° C. The reaction mixture was heated for about another 30 minutes at this temperature. During this time the NCO content dropped to 30.2% by weight. To remove the monomer diisocyanates that were not reacted, the reaction mixture was distilled in a thin-film evaporator. The reaction product (isocyanatoisocyanurate residue of the thin-film evaporation) had an NCO content of 18.5% by weight; the monomer content was <0.7% by weight.
Blocking 500 parts by weight of isocyanatoisocyanurate with 249.3 parts by weight of ε-caprolactam at 90°-130° C. provided a brittle, grindable adduct with a melting range of 89°-93° C. The free NCO content was <0.8% by weight and the practical latent NCO content was about 12.3% by weight.
Table 1 provides a survey of composition, physical and chemical properties of additional blocked isocyanato-isocyanurates.
__________________________________________________________________________
Diisocyanates Melting
MPDI/EBDI NCO Content
*ε-Capro
1H--1,2,4-
NCO Content - Latent
Range
Example IPDI
Mixture
HDI
in % by Weight
lactam
Triazole
in % by Weight
°C.
__________________________________________________________________________
2 532.8
268.8 -- 13.9 37.5 -- 10.1 95-99
3 355.2
403.2 -- 15.9 42.9 -- 11.1 78-82
4 832.5
210 -- 17.6 47.4 -- 11.9 116-118
5 277.5
630 -- 17.1 46.1 -- 11.7 72-75
6 Comparison
444 -- 336
17.5 47.2 -- 11.9 74-79
7 Comparison
832.5
-- 210
17.4 46.9 -- 11.8 100-102
8 444 336 -- 18.0 -- 29.6 13.9 92-97
9 Comparison
444 -- 336
17.5 -- 28.8 13.6 82-86
10 Comparison
-- 1000 -- 19.2 51.8 -- 12.3 58-61
__________________________________________________________________________
Remarks:
*caprolactam test portion in terms of 100 parts by weight of
isocyanatoisocyanurate. The quantities signify parts by weight. The
monomer content following thinfilm distillation was <0.7% by weight.
100 parts by weight of IPDI isocyanurate (IPDI-T 1890 commercial product of the Chem. Werke Huels) with an NCO content of 17.5% by weight and 100 parts by weight of MPDI/EBDI trimer were homogenized at 100°-110° C. The NCO content of the melt amounted to 18.1% by weight. After blocking with the stoichiometric quantity of ε-caprolactam, a solid, well grindable product with a practical latent NCO content of 12.0% by weight and a melting point of 78°-83° C. was obtained.
In conformity with example 11, equal parts of IPDI-T 1890 and HDI trimer were homogenized and then blocked with ε-caprolactam. The solid product had a latent NCO content of 11.9% by weight and a melting range of 66°-72° C.
134 parts by weight of trimethylolpropane were added at 80° C. with vigorous stirring to a mixture consisting of 666 parts by weight of IPDI and 502 parts by weight of an MPDI/EBDI mixture. Following addition, the reaction was heated for another hour at 100° C. and then the nonreacted diisocyanate was removed by thin-film distillation at 160° C./0.1 torr. The process product (residue) had an NCO content of 17.2% by weight; the monomer content was <0.6% by weight.
Blocking with the stoichiometric quantity of ε-caprolactam resulted in a brittle, grindable product with a practical latent NCO content of 11.8% by weight and a melting range of 74°-76° C.
Table 2 provides a survey on composition, chemical and physical properties of additional blocked urethane adducts.
__________________________________________________________________________
Diisocyanates
NCO Content NCO Content
Melting
MPDI/ in % by
*ε-Capro
Latent, in
Range
Example
IPDI
EBDI HDI
Weight lactam
% by Weight
°C.
__________________________________________________________________________
14 999 252 -- 16.2 43.6 11.3 98-104
15 333 756 -- 18.2 48.9 12.2 62-68
16 666 -- 502
17.1 46.1 11.7 65-68
Comparison
17 999 -- 252
16.0 43.1 11.2 85-93
Comparison
__________________________________________________________________________
*Note:
caprolactam test portion in terms of 100 parts by weight of adduct; the
quantities are in parts by weight; the monomer content of the adducts was
<0.7% by weight.
In conformance with example 13, 1,344 parts by weight of MPDI/EBDI mixture and 134 parts by weight of TMP were reacted. The isolated TMP adduct had an NCO content of 17.7% by weight. After blocking with the stoichiometric quantity of ε-caprolactam, a solid product was formed with a latent NCO content of 12% by weight and a melting range of 42°-46° C. The ground cross-linking agent caked after a short time and thus could not be used in powder varnishes.
The urethane adduct on HDI basis produced in conformance with example 13 was soft and stickly after blocking with ε-caprolactam at room temperature.
If the individual urethane adducts are homogenized in the melt in conformance with examples 11 and 12, solid products are isolated whose melting points are about 10° C. lower compared with the "true" urethane adducts.
The initial components--terephthalic acid (Ts), dimethylterephthalate (DMT), hexamethylene glycol (HD), neopentylglycol (NPG), 1,4-dimethylolcyclohexane (DMC) and trimethylolpropane (TMP) were put into a reactor and heated by means of an oil bath. After the substances had been largely melted, 0.05% by weight of di-n-butyltin oxide was added as a catalyst at a temperature of 160° C. The first methanol separtion occurred at a temperature of about 170° C. Within 6-8 hours, the temperature was raised to 220°-230° C. and the reaction was completed within another 12 hours. The polyester was cooled to 200° C. and the volatile parts largely removed within 30-45 minutes by forming a vacuum (1 Hg). During the entire reaction time, the bottom product was stirred and a weak N2 current was directed through the reactin mixture.
The following table reflects polyester compositions and the corresponding physical and chemical characteristics:
______________________________________
Examples 1 2 3
______________________________________
Ts Mol 9 6 8
DMT Mol 9 6 7
HD Mol 3 4 3
NPG Mol 13 5 10
DMC Mol 3 3 2
TMP Mol 1 1 1
OH number mgKOH/g
50-56 48-52 32-36
acid number mgKOH/g
3-4 3-4 3-4
melting point °C.
ca. 70 ca. 80 ca. 85
Second order ca. 50 ca. 55 ca. 60
transition temperature
(DTA) °C.
Viscosity at 160° C.
˜10000
˜15000
˜40000
mPa s
______________________________________
The ground products, cross-linking agents, polyesters, leveling agents* Masterbatch are thoroughly mixed optionally with the white pigment and optionally fillers in an edge mill and then homogenized in the extruder at 100°-130° C. After cooling, the extrudate is crushed and ground by means of a disk mill to a particle size of <100μ. The powder so produced is applied to degreased, optionally prepared sheet iron with an electrostatic powder sprayer at 60 KV and baked in a circulating dried at temperature between 160° and 200° C.
The abbreviations in the following tables denote:
TL=thickness of layer in μm
HK=hardness according to Koenig in sec (DIN 53 157)
HB=hardness according to Buchholz (DIN 53 153)
ET=Erichsen test in mm (DIN 53 156)
CT=cross-cut test (DIN 53 151)
GG 60°<=measurement of gloss according to Gardner (ASTM-D 523)
Imp. rev.=impact reverse in inch·lb
Pigmented Varnish
According to the described process, the powder varnish was produced in accordance with the following formulation, applied and baked between 160° and 200° C.
432.2 parts by weight of polyester according to example B1
171.0 parts by weight of cross-linking agent according to example A1
438.7 parts by weight of white pigment (TiO2)
54.8 parts by weight of leveling agent Masterbatch
__________________________________________________________________________
Baking
conditions Mechanical Characteristics
Time/temperature Imp.
min/°C.
TL HK HB ET CT rev.
GG 60° <)
__________________________________________________________________________
6/200 60-70
182
111
9.6-10
0 60
88
8/200 70 184
125
>10 0 >82
90
10/200 60-70
183
125
>10 0 >82
90
15/180 60-70
180
125
>10 0 >82
86
20/180 65-75
179
125
>10 0 >82
87
25/180 70 179
125
>10 0 >82
90
25/170 60-75
180
111
9.2-9.8
0 50
89
30/170 55-70
179
125
>10 0 70
90
35/160 70-80
181
111
8.7-9.1
0 50
90
__________________________________________________________________________
Pigmented Varnish
According to the described process, the powder varnish was produced in accordance with the following formulation, applied and baked between 160° and 200° C.
493.4 parts by weight of polyester according to example B2
166.6 parts by weight of cross-linking agent according to example A1
480.0 parts by weight of white pigment (TiO2)
60.0 parts by weight of leveling agent Masterbatch
__________________________________________________________________________
Baking
conditions
Mechanical Characteristics
Time/temperature Imp.
min/°C.
TL HK HB ET CT rev.
GG 60° <)
__________________________________________________________________________
6/200 60-75
181
100
9.2-9.9
0 60
88
8/200 70-80
184
111
9.6-10.2
0 >82
90
10/200 70 182
111
>10 0 >82
91
15/180 70 180
111
9.7-10.4
0 >82
89
20/180 70-80
179
125
>10 0 70
89
25/180 65-80
183
111
>10 0 >82
88
25/170 75-80
182
111
9.0-9.5
0 60
89
30/170 70 179
111
>10 0 70
87
35/160 70-80
180
111
8.1-9.1
0 50
88
__________________________________________________________________________
Pigmented Varnish
According to the decribed process, the powder varnish was produced in accordance with the following formulation, applied and baked between 160° and 200° C.
534.6 parts by weight of polyester according to Example B3
125.4 parts by weight of cross-linking agent according to example A1
480.0 parts by weight of white pigment (TiO2)
60.0 parts by weight of leveling agent Masterbatch
__________________________________________________________________________
Baking
conditions
Mechanical Characteristics
Time/temperature Imp.
min/°C.
TL HK HB ET CT rev.
GG 60° <)
__________________________________________________________________________
6/200 80 171
100
8.4-8.7
0 60 68
8/200 70-80
170
100
8.1-8.9
0 70 71
10/200 60-70
172
111
8.8-9.4
0 60 67
15/180 65-80
168
100
7.9-8.1
0 50 70
20/180 70-80
171
100
8.4-8.8
0 70 70
25/180 70-90
169
100
9.2-9.4
0 70 68
25/170 85 170
100
6.7-7.4
0 60 68
30/170 80 171
111
7.5-8.2
0 60 70
35/160 70-85
170
100
5.9-6.2
0 30 71
__________________________________________________________________________
Pigmented Varnish
According to the described process, the powder varnish was produced in accordance with the following formulation, applied and baked between 160° and 200° C.
368.8 parts by weight of polyester according to example B1
181.2 parts by weight of cross-linking agent according to example A2
400.0 parts by weight of white pigment (TiO2)
50.0 parts by weight of leveling agent Masterbatch
__________________________________________________________________________
Baking
conditions
Mechanical Characteristics
Time/temperature Imp.
min/°C.
TL HK HB ET CT rev.
GG 60° <)
__________________________________________________________________________
6/200 80-90
190
100
9.1-9.5
0 60
84
8/200 70-80
194
100
9.9-10.2
0 >82
83
10/200 80-90
189
111
>10 0 >82
86
15/180 75-85
186
100
9.0-9.2
0 40
82
20/180 70-85
190
100
9.7-10.1
0 70
87
25/180 80-90
190
111
>10 0 >82
83
25/170 70-90
188
100
8.7-9.1
0 50
84
30/170 80-90
190
100
9.4-9.9
0 70
84
35/160 70-80
189
100
8.1-9.0
0 50
86
__________________________________________________________________________
Pigmented Varnish
According to the described process, the powder varnish was produced in accordance with the following formulation, applied and baked between 160° and 200° C.
parts by weight of polyester according to example B2
parts by weight of cross-linking agent according to example A2
parts by weight of white pigment (TiO2)
parts by weight of leveling agent Masterbatch
__________________________________________________________________________
Baking
conditions
Mechanical Characteristics
Time/temperature Imp.
min/°C.
TL HK HB ET CT rev.
GG 60° <)
__________________________________________________________________________
6/200 70-80
188
100
9.3-9.8
0 60 82
8/200 70-85
190
100
9.4-9.9
0 70 80
10/200 60-75
187
100
>10 0 >82 84
15/180 70 189
111
8.9-9.1
0 50 84
20/180 80-90
191
100
9.2-9.7
0 70 83
25/180 80 190
111
9.9-10.4
0 >82 80
25/170 60-85
186
100
8.6-9.0
0 50 82
30/170 70-90
188
100
8.7-9.6
0 70 84
35/160 60-80
187
100
7.8-8.4
0 40 85
__________________________________________________________________________
Pigmented Varnish
According to the described process, the powder varnish was produced in accordance with the following formulation, applied and baked between 160° C. and 200° C.
381.2 parts by weight of polyester according to Example B1
168.8 parts by weight of cross-linking agent according to example A3
400.0 parts by weight of white pigment (TiO2)
50.0 parts by weight of leveling agent Masterbatch
__________________________________________________________________________
Baking
conditions
Mechanical Characteristics
Time/temperature Imp.
min/°C.
TL HK HB ET CT rev.
GG 60° <)
__________________________________________________________________________
6/200 70-80
183 100
9.4-9.7
0 70 86
8/200 70-75
186 100
9.8-10.4
0 >82 89
10/200 75-85
186 100
>10 0 >82 90
15/180 80 187 100
8.9-9.6
0 50 89
20/180 70-80
70-80
190
9.4-10
0 70 87
25/180 65-70
187 100
>10 0 >82 89
25/170 70-80
184 100
8.5-9.1
0 40 90
30/170 70 188 100
9.0-9.4
0 70 88
35/160 70-85
186 100
8.0-8.4
0 50 89
__________________________________________________________________________
Pigmented Varnish
According to the described process, the powder varnish was produced in accordance with the following formulation, applied and baked between 160° C. and 200° C.
389.9 parts by weight of polyester according to Example B1
160.1 parts by weight of cross-linking agent according to example A4
400.0 parts by weight of white pigment (TiO2)
50.0 parts by weight of leveling agent Masterbatch
__________________________________________________________________________
Baking
conditions
Mechanical Characteristics
Time/temperature Imp.
min/°C.
TL HK HB ET CT rev.
GG 60° <)
__________________________________________________________________________
6/200 70-80
177
100
9.1-9.5
0 >82 85
8/200 70-80
181
111
9.3-10
0 70 88
10/200 70 180
100
>10 0 >82 84
15/180 60-70
182
100
8.9-9.1
0 60 82
20/180 70 179
100
8.9-9.6
0 70 87
25/180 70-80
181
111
9.7-9.9
0 60 83
25/170 80 178
100
7.9-8.1
0 50 85
30/170 60-70
180
111
8.4-8.8
0 70 85
35/160 60-70
177
100
7.2-8.1
0 40 87
__________________________________________________________________________
Pigmented Varnish
According to the described process, the powder varnish was produced in accordance with the following formulation, applied and baked between 160° C. and 200° C.
373 parts by weight of polyester according to example B3
100 parts by weight of cross-linking agent according to example A5
344 parts by weight of white pigment (TiO2)
43 parts by weight of leveling agent Masterbatch
__________________________________________________________________________
Baking
conditions
Mechanical Characteristics
Time/temperature Imp.
min/°C.
TL HK HB ET CT rev.
GG 60° <)
__________________________________________________________________________
6/200 80-90
169
100
8.0-8.5
0 60
68
8/200 85-95
164
100
8.2-8.9
0 >82
70
10/200 70-80
170
100
8.6-93
0 >82
71
15/180 70 168
100
9.2-9.6
0 >82
66
20/180 60-80
170
100
8.8-9.7
0 >82
68
25/180 70 172
100
8.6-9.5
0 >82
65
25/170 70-80
168
100
7.3-7.9
0 60
69
30/170 80-90
167
100
8.1-8.8
0 70
70
35/160 90 170
100
6.6-7.5
0 40
70
__________________________________________________________________________
Pigmented Varnish
According to the described process, the powder varnish was produced in accordance with the following formulation, applied and baked between 160° C. and 200° C.
389.9 parts by weight of polyester according to example B1
160.1 parts by weight of cross-linking agent according to example A6
400.0 parts by weight of white pigment (TiO2)
50.0 parts by weight of leveling agent Masterbatch
The ready-to-spray powder has lower storage stability and the coating films result in more yellowing under thermal stress.
__________________________________________________________________________
Baking
conditions
Mechanical Characteristics
Time/temperature Imp.
min/°C.
TL HK HB ET CT rev.
GG 60° <)
__________________________________________________________________________
6/200 70-80
172
100
8.9-9.3
0 60 84
8/200 70-90
174
100
9.0-9.8
0 >82 86
10/200 70 176
100
9.7-10
0 >82 83
15/180 70 175
100
8.7-9.3
0 >82 82
20/180 70-80
177
111
>10 0 >82 87
25/180 70 177
100
9.8-10
0 >82 84
25/170 60-70
174
100
8.1-8.4
0 50 83
30/170 65-75
173
111
8.6-9.1
0 70 86
35/160 70-80
172
100
8.4-8.9
0 50 85
__________________________________________________________________________
Pigmented Varnish
According to the described process, the powder varnish was produced in accordance with the following formulation, applied and baked between 160° C. and 200° C.
388 parts by weight of polyester according to example B1
162 parts by weight of cross-linking agent according to example A7
400 parts by weight of white pigment (TiO2)
50 parts by weight of leveling agent Masterbatch
In addition to greater thermo-oxidative instability, greater proneness to chalking was noted following treatment with ultraviolet light.
__________________________________________________________________________
Baking
conditions
Mechanical Characteristics
Time/temperature Imp.
min/°C.
TL HK HB ET CT rev.
GG 60° <)
__________________________________________________________________________
6/200 80 172
100
7.9-8.2
0 50 75
8/200 60-75
175
100
8.0-8.4
0 70 75
10/200 70-80
176
100
8.6-9.1
0 >82 76
15/180 70 177
111
7.5-8.3
0 60 77
20/180 75-90
173
100
7.9-8.1
0 70 76
25/180 70 170
111
8.2-8.6
0 60 77
25/170 60-70
172
100
7.0-7.2
0 40 75
30/170 60-70
174
100
7.5-8.1
0 60 77
35/160 70-80
170
100
6.1-6.4
0 30 76
__________________________________________________________________________
Pigmented Varnish
According to the described process, the powder varnish was produced in accordance with the following formulation, applied and baked between 160° C. and 200° C.
488.9 parts by weight of polyester according to example B1
171.1 parts by weight of cross-linking agent according to example A8
480.0 parts by weight of white pigment (TiO2)
60.0 parts by weight of leveling agent Masterbatch
__________________________________________________________________________
Baking
conditions
Mechanical Characteristics
Time/temperature Imp.
min/°C.
TL HK HB ET CT rev.
GG 60° <)
__________________________________________________________________________
6/200 70-80
187
100
9.1-9.6
0 60 88
8/200 60-75
186
100
9.4-10.1
0 >82 90
10/200 65-70
182
100
>10 0 70 86
15/180 70 188
111
8.8-9.4
0 70 86
20/180 70-80
188
111
9.7 0 >82 88
25/180 80 186
100
>10 0 >82 86
25/170 80 185
111
6.9-7.5
0 40 87
30/170 80-85
188
100
7.8-8.8
0 60 88
35/160 70-85
187
100
6.3-7.5
0 40 85
__________________________________________________________________________
Pigmented Varnish
According to the described process, the powder varnish was produced in accordance with the following formulation, applied and baked between 160° C. and 200° C.
469.1 parts by weight of polyester according to example B1
190.9 parts by weight of cross-linking agent according to example A11
480.0 parts by weight of white pigment (TiO2)
60.0 parts by weight of leveling agent Masterbatch
__________________________________________________________________________
Baking
conditions
Mechanical Characteristics
Time/temperature Imp.
min/°C.
TL HK HB ET CT rev.
GG 60° <)
__________________________________________________________________________
6/200 70-80
180
100
9.2-9.9
0 70
86
8/200 80 181
111
>10 0 >82
89
10/200 60-75
184
125
>10 0 >82
88
15/180 70 180
111
9.7-10.1
0 >82
90
20/180 70 180
111
>10 0 >82
90
25/180 70-80
179
111
>10 0 >82
87
25/170 60-70
182
111
9.3-9.9
0 50
88
30/170 70 178
125
>10 0 70
86
35/160 75-85
181
111
8.5-8.9
0 40
89
__________________________________________________________________________
Pigmented Varnish
According to the described process, the powder varnish was produced in accordance with the following formulation, applied and baked between 160° C. and 200° C.
388 parts by weight of polyester according to example B1
162 parts by weight of cross-linking agent according to example A13
400 parts by weight of white pigment (TiO2)
50.0 parts by weight of leveling agent Masterbatch
__________________________________________________________________________
Baking
conditions
Mechanical Characteristics
Time/temperature Imp.
min/°C.
TL HK HB ET CT rev.
GG 60° <)
__________________________________________________________________________
6/200 60-70
172
111
7.2-7.7
0 70 80
8/200 60 170
125
7.8-8.8
0 >82 82
10/200 70-80
173
111
8.7-9.7
0 70 82
15/180 60-701
172
111
6.3-6.9
0 60 80
20/180 60 174
111
7.5-7.9
0 60 78
25/180 70-80
174
111
8.0-8.1
0 70 83
25/170 70 174
111
6.4-6.8
0 40 83
30/170 70-80
173
111
7.4-7.9
0 70 80
35/160 80 172
100
5.9-6.5
0 30 82
__________________________________________________________________________
Pigmented Varnish
According to the described process, the powder varnish was produced in accordance with the following formulation, applied and baked between 160° C. and 200° C.
465.6 parts by weight of polyester according to example B1
194.4 parts by weight of cross-linking agent according to example A6
480.0 parts by weight of white pigment (TiO2)
60.0 parts by weight of leveling agent Masterbatch
In addition to greater thermo-oxidation instability, greater proneness to chalking was noted also after treatment in ultraviolet light.
__________________________________________________________________________
Baking
conditions
Mechanical Characteristics
Time/temperature Imp.
min/°C.
TL HK HB ET CT rev.
GG 60° <)
__________________________________________________________________________
6/200 60-70
168
100
7.5-8.2
0 70 69
8/200 60-70
170
100
7.9-8.4
0 >82 66
10/200 60-65
169
100
8.7-96
0 >82 70
15/180 70 172
111
5.9-6.0
0 40 68
20/180 70-75
169
111
6.0-6.5
0 50 68
25/180 70-80
170
111
7.1-7.7
0 70 70
25/170 70-80
168
100
5.0-5.3
0 20 69
30/170 80 172
111
6.4-6.9
0 50 67
35/160 70-80
170
100
4.7-5.1
0 10 70
__________________________________________________________________________
Pigmented Varnish
According to the described process, the powder varnish was produced in accordance with the following formulation, applied and baked between 160° C. and 200° C.
428.9 parts by weight of polyester according to example B1
176.1 parts by weight of cross-linking agent according to example A20
440.0 parts by weight of white pigment (TiO2)
55.0 parts by weight of leveling agent Masterbatch
__________________________________________________________________________
Baking
conditions
Mechanical Characteristics
Time/temperature Imp.
min/°C.
TL HK HB ET CT rev.
GG 60° <)
__________________________________________________________________________
6/200 80-90
176
100
7.5-7.7
0 50 77
8/200 80 178
100
8.0 0 60 77
10/200 85-90
177
100
8.2-8.4
0 >82 75
15/180 90-100
180
100
5.7-7.7
0 40 76
20/180 80-90
177
100
6.9-7.4
0 40 78
25/180 80-95
178
111
8.0-8.4
0 70 74
25/170 90-100
178
100
6.2-6.7
0 30 75
30/170 90 180
100
7.1-7.7
0 50 75
35/160 80-95
179
100
5.7-6.4
0 20 77
__________________________________________________________________________
Two epoxy resins based on an adduct made of 2,2-bis(4-hydroxylphenyl)propane (Dian) and epichlorohydrin were used, which were first subjected to HCl separation and then reacted with additional Dian.
According to information from the manufacturer, the epoxy resins had the following physical data:
______________________________________
D 1.1 EP equivalent weight
90-1000
EP value 0.10-0.11
OH value 0.34
Melting range 96-104° C.
D 1.2 EP equivalent weight
1700-2000
EP value 0.05-0.059
OH value 0.36
Melting range 125-132° C.
______________________________________
Pigmented Varnish
According to the process described in example C, the powder varnish with the following recipe was produced, applied and baked between 180°-200° C.
87.9 parts by weight of epoxy according to example D 1.1
110.4 parts by weight of epoxy according to example D 1.2
126.7 parts by weight of cross-linking agent according to A1
150.0 parts by weight of white pigment (TiO2) 25.0 parts by weight of leveling agent Masterbatch (10% Modaflow in epoxy according to D 1.1)
__________________________________________________________________________
Baking
conditions
Mechanical Characteristics
Time/temperature Imp.
min/°C.
TL HK HB ET CT rev.
GG 60° <)
__________________________________________________________________________
15/200 60-70
193
111
5.7-7.0
0 40 84
20/200 70 195
111
6.4-8.0
0 60 86
25/180 70-80
190
111
5.2-6.8
0 30 85
30/180 65-80
197
111
6.7-7.1
0 50 85
__________________________________________________________________________
Pigmented Varnish
According to the process described in example C, the powder varnish with the following recipe was produced, applied and baked between 180° C.-200° C.
108.4 parts by weight of epoxy according to example D 1.2
85.9 parts by weight of epoxy according to example D 1.1
130.7 parts by weight of cross-linking agent according to A13
150.0 parts by weight of white pigment (TiO2)
25.0 parts by weight of leveling agent Masterbatch (10% Modaflow in epoxy according to D 1.1)
__________________________________________________________________________
Baking
conditions
Mechanical Characteristics
Time/temperature Imp.
min/°C.
TL HK HB ET CT rev.
GG 60° <)
__________________________________________________________________________
15/200 60 192
111
5.8-6.0
0 30 83
20/200 60-75
187
111
6.1-7.8
0 70 83
25/180 70-80
193
111
5.5-6.5
0 20 85
30/180 65-75
190
111
6.2-7.1
0 50 84
__________________________________________________________________________
Having now fully described this invention, it will be apparent to one of ordinary skill in the art that many changes and modifications can be made thereto without departing from the spirit or scope of the invention as set forth herein.
Claims (12)
1. A mixture of substances suitable as a powder varnish or a binder for powder varnishes consisting essentially of an isocyanate component with partially or totally blocked isocyanate groups, and a polyhydroxyl component, wherein mixed trimers or mixtures of individual trimers are used as the isocyanate component from a mixture consisting essentially of 2-methyl-1,5-diisocyanatopentane (MPDI) and 2-ethyl-1,4-diisocyanatobutane (EBDI) having the formulas: ##STR3## in the amounts of about 88 to 99% by weight of (MPDI) and about 12 to 1% by weight of (EBDI), in combination with 3-isocyanato-3,5,5-trimethyl-cyclohexylisocyanate (IPDI) or mixed urethane adducts or a mixture of individual urethane adducts obtained from the reaction of the MPDI/EBDI mixture in combination with IPDI with diols or triols or a mixture thereof.
2. The mixture of substances suitable as a powder varnish or as a binder for powder varnishes as in claim 1, wherein the ratio of the diisocyanate mixture MPDI/EBDI to IPDI, used for trimerization or urethane adduct formation, is between about 90 and 10% by weight and 10 and 90% by weight, respectively.
3. The mixture of substances suitable as a powder varnish or as a binder for powder varnishes as in claim 2, wherein said ratio is between about 75 and 25% by weight and 25 and 75% by weight, respectively.
4. The mixture of substances suitable as a powder varnish or as a binder for powder varnishes as in claim 1, wherein said blocked isocyanate component has a latent NCO content of about 7-18% by weight and a free NCO content of less than or equal to 3% by weight.
5. The mixture of substances suitable as a powder varnish or as a binder for powder varnishes as in claim 4, wherein said blocked isocyanate component has a latent NCO content of about 9-15% by weight and a free NCO content of less than or equal to 2% by weight.
6. The mixture of substances suitable as a powder varnish or as a binder for powder varnishes as in claim 1, wherein said trimer is an isocyanurate trimer having a NCO content of about 14-22% by weight and said urethane adduct has a NCO content of about 11-19% by weight.
7. The mixture of substances suitable as a powder varnish or as a binder for powder varnishes as in claim 6, wherein said isocyanurate trimer has a NCO content of 15.0-20.5% by weight and the urethane adduct has a NCO content of 13-17% by weight.
8. The mixture of substances suitable as a powder varnish or as a binder for powder varnishes as in claim 1, wherein said trimers have about 30-50% of the NCO groups reacted.
9. The mixture of substances suitable as a powder varnish or as a binder for powder varnishes as in claim 1, wherein said diol or triol is trimethylolpropane.
10. The mixture of substances suitable as a powder varnish or as a binder for powder varnishes as in claim 1, wherein said polyhydroxyl component is selected from the group consisting of polyesters, epoxy resins and acrylates containing hydroxyl groups, having a molecular weight of about 800-10,000.
11. The mixture of substances suitable as a powder varnish or a binder for powder varnishes as in claim 1, wherein said polyesters are the polyesters of terephthalic acid with the alcohols hexamethylene glycol, neopentyl glycol, 1,4-dimethanolcyclohexane and 2,2,2-trimethylolpropane.
12. The mixture of substances suitable as a powder varnish or as a binder for powder varnishes as in claim 1, wherein said isocyanate component is blocked by ε-caprolactam and 1H-1,2,4-triazole.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3322718 | 1983-06-24 | ||
| DE19833322718 DE3322718A1 (en) | 1983-06-24 | 1983-06-24 | AS POWDER LACQUER OR BINDING AGENT FOR POWDER VARNISHES SUITABLE MIXTURE |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US4500697A true US4500697A (en) | 1985-02-19 |
Family
ID=6202240
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US06/622,180 Expired - Fee Related US4500697A (en) | 1983-06-24 | 1984-06-19 | Mixture of substances suitable for use as a powder varnish or binder for powder varnishes |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US4500697A (en) |
| EP (1) | EP0132518B1 (en) |
| JP (1) | JPS6047079A (en) |
| AT (1) | ATE24008T1 (en) |
| DE (2) | DE3322718A1 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5939199A (en) * | 1996-03-26 | 1999-08-17 | Huels Aktiengesellschaft | Process for the preparation of heat curable weather-resistant polyurethane powder coatings, and the coatings thus obtained |
| US6051675A (en) * | 1996-07-04 | 2000-04-18 | Huels Aktiengesellschaft | Blocked polyisocyanates, a process for their preparation, and their use |
| US20030104181A1 (en) * | 2001-12-05 | 2003-06-05 | Degussa Ag | Use of polyurethane powder coating materials |
| WO2006050938A1 (en) * | 2004-11-10 | 2006-05-18 | Insa (Institut National Des Sciences Appliquees) | Two-part polyisocyanate/polyol composition and its use for making casted products, in particular ophthalmic lenses |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5048890A (en) * | 1989-05-26 | 1991-09-17 | Aisin Seiki Kabushiki Kaisha | Guide rail for a sliding roof apparatus |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4354014A (en) * | 1979-07-19 | 1982-10-12 | Chemische Werke Huls Aktiengesellschaft | Powdered coating compositions having good storage stability and production of same |
| US4383076A (en) * | 1979-09-26 | 1983-05-10 | Elmar Wolf | Single component enamels based on blocked polyisocyanurate polyisocyanates |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2551634C3 (en) * | 1975-11-18 | 1980-07-17 | Bayer Ag, 5090 Leverkusen | Process for the preparation of polyisocyanates containing isocyanurate groups |
| DE2842641A1 (en) * | 1978-09-29 | 1980-04-10 | Bayer Ag | Poly-isocyanate used as hardener for polyurethane lacquer - prepd. from 1-isocyanato-3,3,5-tri:methyl-5-isocyanato:methyl-cyclohexane and contg. trimerised, blocked and free isocyanate gps. |
| DE2929224A1 (en) * | 1979-07-19 | 1981-02-05 | Huels Chemische Werke Ag | PRODUCTION OF FREE NCO GROUPS CONTAINING ISOPHORONE DIISOCYANATE ADDUCTS CONTAINED WITH EPSILON-CAPROLACTAM, AND COMPOUNDS THEREFORE |
| DE3033860A1 (en) * | 1980-09-09 | 1982-04-15 | Bayer Ag, 5090 Leverkusen | NEW ISOCYANATO-ISOCYANURATE, A METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS ISOCYANATE COMPONENT IN POLYURETHANE PAINTS |
| DE3151854A1 (en) * | 1981-12-30 | 1983-07-07 | Chemische Werke Hüls AG, 4370 Marl | THERMAL AND OXIDATION RESISTANT POLYURETHANE COATINGS |
-
1983
- 1983-06-24 DE DE19833322718 patent/DE3322718A1/en not_active Withdrawn
-
1984
- 1984-04-30 AT AT84104852T patent/ATE24008T1/en not_active IP Right Cessation
- 1984-04-30 DE DE8484104852T patent/DE3461538D1/en not_active Expired
- 1984-04-30 EP EP84104852A patent/EP0132518B1/en not_active Expired
- 1984-06-19 US US06/622,180 patent/US4500697A/en not_active Expired - Fee Related
- 1984-06-22 JP JP59127655A patent/JPS6047079A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4354014A (en) * | 1979-07-19 | 1982-10-12 | Chemische Werke Huls Aktiengesellschaft | Powdered coating compositions having good storage stability and production of same |
| US4383076A (en) * | 1979-09-26 | 1983-05-10 | Elmar Wolf | Single component enamels based on blocked polyisocyanurate polyisocyanates |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5939199A (en) * | 1996-03-26 | 1999-08-17 | Huels Aktiengesellschaft | Process for the preparation of heat curable weather-resistant polyurethane powder coatings, and the coatings thus obtained |
| US6051675A (en) * | 1996-07-04 | 2000-04-18 | Huels Aktiengesellschaft | Blocked polyisocyanates, a process for their preparation, and their use |
| US6166164A (en) * | 1996-07-04 | 2000-12-26 | Huels Aktiengesellschaft | Blocked polyisocyanates, a process for their preparation, and their use |
| US6437074B1 (en) | 1996-07-04 | 2002-08-20 | Huels Aktiengesellschaft | Blocked polyisocyanates, a process for their preparation, and their use |
| US20030104181A1 (en) * | 2001-12-05 | 2003-06-05 | Degussa Ag | Use of polyurethane powder coating materials |
| US6827971B2 (en) * | 2001-12-05 | 2004-12-07 | Degussa Ag | Use of polyurethane powder coating materials |
| WO2006050938A1 (en) * | 2004-11-10 | 2006-05-18 | Insa (Institut National Des Sciences Appliquees) | Two-part polyisocyanate/polyol composition and its use for making casted products, in particular ophthalmic lenses |
| US20080090989A1 (en) * | 2004-11-10 | 2008-04-17 | Insa (Institut National Des Sciences Appliquees | Two-Part Polyisocyanate/Polyol Composition and Its Use for Making Casted Products, in Particular Ophthalmic Lenses |
Also Published As
| Publication number | Publication date |
|---|---|
| DE3461538D1 (en) | 1987-01-15 |
| ATE24008T1 (en) | 1986-12-15 |
| EP0132518B1 (en) | 1986-12-03 |
| DE3322718A1 (en) | 1985-01-03 |
| JPS6047079A (en) | 1985-03-14 |
| EP0132518A1 (en) | 1985-02-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4246380A (en) | Powdery polyurethane lacquers based on polyester resins and blocked isocyanates | |
| US4495229A (en) | One-component, heat-curing polyurethane-coatings, stable in storage | |
| US6051675A (en) | Blocked polyisocyanates, a process for their preparation, and their use | |
| US5554701A (en) | Crosslinked polyesters made from decahydronaphthalene dimethanol | |
| US5916629A (en) | Heat-curing, one-component adhesives which are based on polyurethanes, a process for their preparation, and their use | |
| US4500697A (en) | Mixture of substances suitable for use as a powder varnish or binder for powder varnishes | |
| US5464921A (en) | Polyisocyanate mixtures, a process for their production and their use for the production of polyurethanes | |
| CN1986591A (en) | Preparation method of polyaddition compound | |
| US4782128A (en) | Polyurethane powder coating compositions which yield a matte surface after setting | |
| US4500696A (en) | Powder surface coatings | |
| AU758145B2 (en) | Powder coating crosslinking agents containing uretdione group s and free isocyanate | |
| US4920173A (en) | PUR powder paints for matt coatings | |
| US5331078A (en) | Blocked highly functional polyisocyanate adducts, a process for the preparation thereof and the use thereof | |
| JPH1087784A (en) | Polyisocyanate bearing both urea group and uretedione group, its production and polyurethane-lacquer system | |
| US4952632A (en) | Trans-cyclohexane-1,4-diisocyanate which is completely or partially blocked with epsilon-caprolactam; and the manufacture and use of the same | |
| US5939199A (en) | Process for the preparation of heat curable weather-resistant polyurethane powder coatings, and the coatings thus obtained | |
| EP0132513B1 (en) | One-component stoving varnish | |
| US6204351B1 (en) | Blocked polyisocyanates with built-in hals stabilizer | |
| US5919568A (en) | Powder coating and its use for coating heat-resistant substrates | |
| US5874173A (en) | Heat-curing, solvent-free one-component adhesives which are based on polyurethanes and which do not give off elimination products, a process for their preparation, and their use | |
| CA2210272A1 (en) | Heat-curing solvent-free one-component adhesive which is based on polyurethanes and which does not give off elimination products, and its use | |
| US5945531A (en) | Polyisocyanates containing uretdione groups | |
| JPH11140158A (en) | Partially or entirely blocked polyisocyanate, production of the compound, and transparent or pigmented powder coating material | |
| EP0703257A1 (en) | Process for the preparation of thermosetting, weatherable polyurethane powder compositions | |
| CA2213547A1 (en) | Acetophenone oxime-blocked pu powder coatings and their use |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| AS | Assignment |
Owner name: CHEMISCHE WERKE HULS AKTIENGESELLSCHAFT,GERMANY Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:DISTELDORF, JOSEF;GRAS, RAINER;SIGNING DATES FROM 19840528 TO 19840530;REEL/FRAME:004334/0396 Owner name: CHEMISCHE WERKE HULS AKTIENGESELLSCHAFT, POSTFACH Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNORS:DISTELDORF, JOSEF;GRAS, RAINER;REEL/FRAME:004334/0396;SIGNING DATES FROM 19840528 TO 19840530 |
|
| FEPP | Fee payment procedure |
Free format text: PAYOR NUMBER ASSIGNED (ORIGINAL EVENT CODE: ASPN); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY |
|
| FPAY | Fee payment |
Year of fee payment: 4 |
|
| FPAY | Fee payment |
Year of fee payment: 8 |
|
| REMI | Maintenance fee reminder mailed | ||
| LAPS | Lapse for failure to pay maintenance fees | ||
| FP | Lapsed due to failure to pay maintenance fee |
Effective date: 19970219 |
|
| STCH | Information on status: patent discontinuation |
Free format text: PATENT EXPIRED DUE TO NONPAYMENT OF MAINTENANCE FEES UNDER 37 CFR 1.362 |